Naphthalene Dicarboxylic Acid Research Articles

Zirconium-based hydrophobic-MOFs as innovative electrode modifiers for flibanserin determination: Exploring the electrooxidation mechanism using a comprehensive spectroelectrochemical study.

Threedifferent types of Zr-based MOFs derived from benzene dicarboxylic acid (BDC) and naphthalene dicarboxylic acid as organic linkers (ZrBDC, 2,6-ZrNDC, and 1,4-ZrNDC) were synthesized. They were characterized using X-ray diffraction analysis (XRD), X-ray photoelectron spectroscopy (XPS), Fourier-transform IR spectroscopy (FT-IR), and Transmission electron microscopy (TEM). Their hydrophilic/hydrophobic nature was investigated via contact angle measurements; ZrBDC MOF was hydrophilic and the other two (ZrNDC) MOFs were hydrophobic. The three MOFs were combined with MWCNTs as electrode modifiers for the determinationof a hydrophobic analyte, flibanserin (FLB), as a proof-of-concept analyte. Under the optimized experimental conditions, a significant enhancement in the oxidation peak current of FLB was observed when utilizing 2,6-ZrNDC and 1,4-ZrNDC, being the highest when using 1,4-ZrNDC. Furthermore, a thorough investigation of the complex oxidation pathway of FLB was performed by carrying out simultaneous spectroelectrochemical measurements. Based on the obtained results, it was verified that the piperazine moiety of FLB is the primary site for electrochemical oxidation. The fabricated sensor based on 1,4-ZrNDC/MW/CPE showed an oxidation peak of FLB at 0.8V vs Ag/AgCl. Moreover, it showed excellent linearity for the determinationof FLB in the range 0.05 to 0.80μmol L-1 with a correlation coefficient (r) = 0.9973 and limit of detection of 3.0nmol L-1. The applicability of the developed approach was demonstrated by determinationof FLB in pharmaceutical tablets and human urine samples with acceptable repeatability (% RSD values were below 1.9% and 2.1%, respectively) and reasonable recovery values (ranged between 97 and 103% for pharmaceutical tablets and between 96 and 102% for human urine samples). The outcomes of the suggested methodology can be utilized for the determinationof other hydrophobic compounds of pharmaceutical or biological interest with the aim of achieving low detection limits of these compounds in various matrices.

Europium metal organic frameworks: Chemical and Optical properties

This paper presents the results of synthesizing five metalorganic frameworks (MOFs) of europium with luminescent properties using a stirring methodology at room temperature. The materials were obtained using the organic linkers benzene dicarboxylic acid (BDC), benzene tricarboxylic acid (BTC), naphthalene dicarboxylic acid (NDC), amino benzene dicarboxylic acid (BDC-NH2) and hydroxybenzene dicarboxylic acid (BDC-OH). XRD and FTIR determined structural and optical properties, and, for three of the materials, SEM. The MOFs obtained have a crystal size of the order of nanometers and presented characteristic functional groups of organic linkers. Optical properties were determined by luminescence spectroscopy, and emission and excitation spectra were obtained. The photoluminescence data of the MOFs showed that the organic linkers were useful for the energy transfer to the lanthanide ion (antenna effect). The material with the highest emission was Eu₂BDC₃, and the one with the lowest was Eu₂(BDC-NH₂)₃. The latter did not present a defined crystalline structure. The Eu₂(BDC-NH₂)₃ and Eu₂(BDC-OH)₃ structures suffered the loss of emission over time. The materials with the highest emission can be used as chemical sensors, cell tracers, and electronic components, including some of their applications.

Two Cd(II)-based metal-organic frameworks as difunctional fluorescence sensors to detect enrofloxacin and Fe3+

Two ternary Cd(II) metal-organic frameworks [Cd4(L)2(2,6-NDA)4·5H2O]n (1) and [Cd(L)0.5(1,8-NDA)·0.75H2O]n (2) (L ​= ​1,4-bis(1-(piperidin-4-ylmethyl)-1H-benzo[d]imidazole-2-yl)butane, 2,6-H2NDA ​= ​2,6-naphthalenedicarboxylic acid, 1,8-H2NDA ​= ​1,8-naphthalenedicarboxylic acid) were synthesized based on the L and two isomeric naphthalene dicarboxylic acids. 1 and 2 exhibit a 3D 4,4T11 and a 2D 3,4L13 network, respectively. Both 1 and 2 show remarkable thermal stability and can be used as difunctional fluorescence sensors for Fe3+ and enrofloxacin via a fluorescence quenching process with high sensitivity and selectivity. In addition, the fluorescence sensing mechanism was discussed in detail.

Synthesis of Fe-MOFs/h-CeO2 hollow micro-spheres and their highly efficient photocatalytic degradation of RhB

A series of Fe-MOFs/h-CeO2 composite photocatalysts were synthesized by a hydrothermal method using cerium oxide hollow microspheres as carriers, naphthalene dicarboxylic acid as an organic ligand, and iron as a metal center. The obtained samples were characterized by XRD, SEM, TEM, UV-Vis, XPS, and PL. It shows that the samples contained hollow CeO2 microspheres with a diameter of about 500 nm as the carrier, and the surface was a burr-like shell coated with Fe-MOFs about 100 nm. The bandgap of Fe-MOFs/h-CeO2 was reduced to 1.62 eV; the photocatalytic performance was tested via RhB degradation. The results indicate that the Fe-MOFs/h-CeO2 composites show enhanced photocatalytic activity, in contrast with CeO2 hollow microspheres. All of this can be attributed to the that the MOFs fabricated could not only improve the light adsorption through the outer shells and provide more active sites but also enhance charge carriers. It is expected that this study could provide helpful results for fabricating and exploration of composite catalysts with tunable photocatalytic performance.

Efficient Polyester Hydrogenolytic Deconstruction via Tandem Catalysis.

Using a mechanism-based solvent-free tandem catalytic approach, commodity polyester plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) are rapidly and selectively deconstructed by combining the two air- and moisture-stable catalysts, Hf(OTf)4 and Pd/C, under 1 atm H2 , affording terephthalic acid (or naphthalene dicarboxylic acid for PEN) and ethane (or butane for PBT) in essentially quantitative yield. This process is effective for both laboratory grade and waste plastics, and comingled polypropylene remains unchanged. Combined experimental and DFT mechanistic analyses indicate that Hf(OTf)4 catalyzes a mildly exergonic retro-hydroalkoxylation reaction in which an alkoxy C-O bond is first cleaved, yielding a carboxylic acid and alkene, and this process is closely coupled to an exergonic olefin hydrogenation step, driving the overall reaction forward.

Efficient Polyester Hydrogenolytic Deconstruction via Tandem Catalysis

AbstractUsing a mechanism‐based solvent‐free tandem catalytic approach, commodity polyester plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) are rapidly and selectively deconstructed by combining the two air‐ and moisture‐stable catalysts, Hf(OTf)4 and Pd/C, under 1 atm H2, affording terephthalic acid (or naphthalene dicarboxylic acid for PEN) and ethane (or butane for PBT) in essentially quantitative yield. This process is effective for both laboratory grade and waste plastics, and comingled polypropylene remains unchanged. Combined experimental and DFT mechanistic analyses indicate that Hf(OTf)4 catalyzes a mildly exergonic retro‐hydroalkoxylation reaction in which an alkoxy C−O bond is first cleaved, yielding a carboxylic acid and alkene, and this process is closely coupled to an exergonic olefin hydrogenation step, driving the overall reaction forward.

Sustainable Synthesis of Functionalized Naphthalenedicarboxylic Acid from Lignocellulose-Derived Platform Chemicals

Sustainable Synthesis of Functionalized Naphthalenedicarboxylic Acid from Lignocellulose-Derived Platform Chemicals

Friedländer, Knoevenagel, and Michael Reactions Employing the Same MOF: Synthesis, Structure, and Heterogeneous Catalytic Studies of ([Zn(1,4-NDCA)(3-BPDB)0.5]·(DMF)(MeOH) and [Cd4(1,4-NDCA)4(3-BPDB)4]·2(DMF)

Two new inorganic–organic coordination polymers, namely, ([Zn(1,4-NDCA)(3-BPDB)0.5]·(DMF)(MeOH) (I) and [Cd4(1,4-NDCA)4(3-BPDB)4]·2(DMF) (II), were synthesized by employing naphthalene dicarboxylic acid and 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (3-BPDB) ligands. Both the compounds have a three-dimensional structure and exhibit Lewis acidic as well as basic characters. The Lewis acid character was explored by using the Friedländer reaction involving the condensation of amino benzaldehyde and ketones. The Lewis basic character was investigated by employing a three-component condensation that combines Knoevenagel and Michael reactions. Both the Lewis acid and Lewis base reactions were found to proceed well, giving rise to the expected products with good and comparable yields of ∼80%. The catalysts were found to be active for up to three cycles.

A stable nitrogen-rich zinc-based metal organic framework to investigate the structural similarity effect on the sorption efficiency of nitrogen-containing compounds

A stable porous zinc-based metal organic framework (MOF) containing nitrogen-rich bis-tetrazolate ligand was synthesized to study the role of similar structures concerning both extractive phase and the desired solutes to achieve greater sorption efficiency. With implementing a dispersive micro-solid phase extraction (d-µ-SPE) methodology, the sorption capability and influencing structural parameters i.e., porosity, surface area and interactions types were investigated for the synthesized zinc-bis-tetrazolate (ZnBT) MOF and compared with some synthesized sorbents such as MIL-101, MIL-101-NH2, cadmium naphthalene dicarboxylic acid dimethyl formamide [Cd(NDC)(DMF)], polyaniline and LiChrolut® EN. The sorption trends for triazines, as nitrogen-containing analytes, and benzene homologs, as nitrogen-free compounds, were evaluated. Accordingly, the synthesized ZnBT nanostructure was significantly dominant for the isolation of triazines. Moreover, the observed moderate sorption efficiency of nitrogen-rich MOF toward BTEX verifies the significant role of similar nitrogen-rich structure between MOF and triazines. Eventually, ZnBT was employed as the desired extractive phase for d-µ-SPE of triazines from environmental water samples followed by gas chromatography-mass spectrometric quantification. Under the optimized conditions, limits of detection (S/N = 3) and limits of quantification (S/N = 10) were in the ranges of 2–10 and 6–30 ng L−1, respectively. Also, the linear dynamic range (6–1000 ng L−1) and intra-day (3.3–5.2%) and inter-day (5.5–6.8%) relative standard deviations were comparable with other relevant reports. Among the selected triazines, a quantity of 51 ng L−1 of atrazine was quantified in the paddy water sample B. The obtained relative recovery values of 89–98% at 50 and 500 ng L−1 levels, confirmed the insignificant matrix effect.

Interaction of metal organic framework with fluorinated polymer on ceramic hollow fiber

Zirconium-based metal–organic framework (Zr-based MOF) often appears as a highly stable material in terms of thermal and chemical aspects. However, intrinsic defects that occur in its framework lead to poor membrane performance, which hinders its amazing properties. Therefore, a new approach in preparing UiO-66-NDC (UiO: University of Oslo, NDC: naphthalenedicarboxylic acid) membrane supported on ceramic hollow fibre was designed to tackle such problems. Polymerising the MOF active layer using ultraviolet curable resin (UCR) improved the original UiO-66-NDC framework, resulting in perfect octahedron crystal morphology and smoother and densely packed integrated layers, as shown through FESEM and AFM. XPS results reveal that the photopolymerisation process lengthened the UiO-66-NDC chain during the reaction, which then supplied additional atoms from UCR to the missing linker position inside UiO-66-NDC framework. The negative water flux turned to positive water flux (from −718.820 to 16.189 L/m2∙h), with a sharp decrement in reverse solute flux (from 34.194 to 0.007 kg/m2∙h) in the forward osmosis (FO) test.

Secondary Metabolites from the Leather Coral-Derived Fungal Strain Xylaria sp. FM1005 and Their Glycoprotein IIb/IIIa Inhibitory Activity.

Five new tyrosine derivatives (1-5), one new phenylacetic acid derivative (6), two new quinazolinone analogues (7 and 8), one new naphthalenedicarboxylic acid (9), and one new 3,4-dihydroisocoumarin derivative (10), together with seven known compounds, were isolated from the fungus Xylaria sp. FM1005, which was isolated from Sinularia densa (leather coral) collected in the offshore region of the Big Island, Hawaii. The structures of compounds 1-10 were elucidated by extensive analysis of NMR spectroscopy, HRESIMS, and ECD data. Due to their structure similarity to the antiplatelet drug tirofiban, compounds 1-5 together with 6 were investigated for their antithrombotic activities. Compounds 1 and 2 strongly inhibited the binding of fibrinogen to purified integrin IIIb/IIa in a dose-dependent manner with the IC50 values of 0.89 and 0.61 μM, respectively, and compounds 1 and 2 did not show any cytotoxicity against A2780 and HEK 293 at 40 μM.

Fabrication and characterization of a novel terpolyester film: An alternative substrate polymer for flexible electronic devices

Designing and development of flexible electronic devices require a detailed investigation of the substrate materials available for the fabrication of the devices. This research work reports the fabrication of a novel film with a copolyester of high trans-1,4-cyclohexandimethanol, terephthalic acid, and naphthalene dicarboxylic acid (PCTN) using melt extrusion. The synthesized amorphous film was uniaxially stretched and thoroughly characterized for their mechanical, thermal, thermo-mechanical, water barrier, and optical (birefringence) properties. Universal testing machine (UTM) and differential scanning calorimetry (DSC) results showed that developed film was having good mechanical and thermal properties, with exceptional dimensional stability, which was confirmed by the thermo-mechanical analyzer (TMA). Results indicated that analyzed properties increase with the increase in the draw ratio (DR). This is due to the increase in the orientation polymeric chains inside the films which were verified by DSC and X-ray diffraction (XRD). Additionally, PCTN film has lower water barrier and birefringence properties compared to conventional polymers such as poly (ethylene terephthalate) (PET), poly (ethylene 2,6-naphthalate) (PEN), and polyimide (PI) films. Based on the exceptional performance properties, novel PCTN film may find a strong position as a substrate for next-generation flexible electronics among various performance materials.

Synthesis and characterization of a novel microporous lanthanide based metal-organic framework (MOF) using napthalenedicarboxylate acid

A novel metal-organic framework based on naphthalenedicarboxylic acid is described. By solvothermal reaction method, 2,6-Naphthalenedicarboxylic acid, existing organic ligands that have never been used to support La-MOFs, was synthesized using acetic acid as the solvent and lanthanum nitrate hexahydrate as a metal source. So far, this type of metal-organic framework based lanthanum ion has not been investigated before. La-NDC MOFs were characterized to determine its functional groups contained in La-MOFs, morphology and particle size, crystallinity, optical and thermal stability by SEM (Scanning Electron Microscopy), FTIR (Fourier transform infrared) spectroscopy, XRD (X-ray Diffraction), UV-vis and TGA (thermogravimetric analysis) sequencely. The adsorption/desorption isotherms of N2 were measured at 77.4 K to know the specific surface area and pore volume of La-NDC MOF. BET (Brunauer-Emmet-Teller) equation was also applied to calculate the surface area of compounds.

Influence of the substitution pattern of four naphthalenedicarboxylic acids on the structures and properties of group 13 metal-organic frameworks and coordination polymers.

Metal-organic frameworks containing Ga3+ ions and four differently substituted naphthalenedicarboxylates (ndc2-) have been synthesized and characterized. The Ga3+ ions are six-fold coordinated by oxygen atoms in all title compounds, but two different inorganic building units, i.e. trans corner-sharing and cis,trans edge-sharing octahedra are observed. Crystal structures were validated by Rietveld refinements against powder X-ray diffraction data. [Ga(OH)(1,4-ndc)]·2H2O crystallizes in a non-breathing MIL-53 type structure with two different pore sizes (5.5 × 5.5 Å and 9 × 9 Å). It is non-porous with respect to nitrogen but has a water adsorption capacity of about 155 mg g-1 and a thermal stability of up to 240 °C. The dense compound [Ga(OH)(1,8-ndc)] crystallizes in a new layered structure motif, which is related to the crystal structure of MIL-122 ([Al(OH)((O2C)4C6H2)]). The third and fourth compounds [Ga2(OH)4(2,3-ndc)]·H2O and [Ga(OH)(2,6-ndc)]·H2O are isoreticular to CAU-15 ([Al2(OH)4(2,3-bdc)]·H2O) and MIL-69 ([Al(OH)(2,6-ndc)]·H2O), respectively. The last two compounds are non-porous toward nitrogen but reversible dehydration was demonstrated. For comparison, the two new compounds [Al(OH)(1,8-ndc)] and [Al2(OH)4(2,3-ndc)]·H2O, which are isostructural to the newly described gallium compounds, were also synthesized and fully characterized. The Al-containing coordination polymers exhibit higher temperature stabilities compared to their isostructural Ga compounds.

Nanodispersions stabilized by β-cyclodextrin nanosponges: application for simultaneous enhancement of bioactivity and stability of sage essential oil

The aim of this work was to stabilize oil-in-water nanoemulsion containing sage (salvia officinalis) essential oil, for enhancing its physicochemical stability and enlarging its industrial applications. New β-cyclodextrin nanosponges were synthesized by polycondensation using naphthalene dicarboxylic acid as cross-linking agent, the latter system was characterized by FTIR spectroscopy, SEM, BET, and powder XRD. Nanoemulsions stabilized by free β-cyclodextrin or nanosponges were prepared, their physicochemical properties were determined (particles size, zeta potential, viscosity, turbidity, and essential oil content) and their stability was studied at different storage temperatures (4 °C, 20 °C, and 40 °C) during 3 months. Pharmaceutical application of prepared nanoemulsions was investigated in vitro by dissolution test study and in vivo by their antidiabetic activity evaluation in rats. Sage essential oil nanoemulsion stabilized by β-cyclodextrin-naphthalene dicarboxylic acid nanosponges presents very high stability and promising uses in pharmaceutical industry.

Six uranyl-organic frameworks with naphthalene-dicarboxylic acid and bipyridyl-based spacers: syntheses, structures, and properties.

A new series of uranium coordination polymers have been hydrothermally synthesized by using 1,4-naphthalene dicarboxylic acid (H2NDC), namely, (H3O)2[(UO2)2(NDC)3]·H2O (1), (H2-bpp)[(UO2)2(NDC)3]·EtOH·5H2O (2), (H2-bpe)2/2[(UO2)2(NDC)3]·EtOH (3), (H2-bpp)[(UO2)2(NDC)3]·5H2O (4), (H2-bpp)[(UO2)(HNDC)(NDC)]2·2H2O (5), and (H2-bpy)[(UO2)(NDC)2] (6) [bpp = 1,3-di(4-pyridyl) propane, bpe = 4,4'-vinylenedipyridine, bpy = 4,4'-bipyridine]. Single-crystal X-ray diffraction demonstrates that complex 1 represents the uranyl-organic polycatenated framework derived from a simple two-dimensional honeycomb grid network structure via a H2NDC linker. Complexes 2-4 contain the dinuclear motifs of the two UO7 pentagonal and one UO8 hexagonal bipyramids which are linked by NDC2- anions creating a (UO2)4(NDC)2 unit, and further extend to a 2D layer through NDC2- anions. Complex 5 displays a 1D zigzag double chain structure, in which the carboxylate groups of the NDC2- anions adopt a chelate mode and further extends to a 2D framework via hydrogen bonds. The 1D structure of complex 6 is similar to the zigzag chain of complex 5. In addition, powder X-ray diffraction, elemental analysis, IR, thermal stability and luminescence properties of all complexes have also been investigated in this paper. The photocatalytic properties of the six complexes for the degradation of tetracycline hydrochloride (TC) under UV irradiation have been examined. Moreover, density functional theory (DFT) calculations were carried out to explore the electronic structural and bonding properties of the uranyl complexes 1-6.

Interplay Between π-Stacking and Hydrogen Bonding in the Self-Association of Different Isomers of Naphthalenedicarboxylic Acid

Using proton and carbon chemical shifts, we investigated the self-association of three isomers of naphthalenedicarboxylic acid, a model for the aggregation of asphaltenes. Experimental proton chemical shifts of each isomer were measured as a function of concentration in an aprotic solvent. Several potential structures of the monomer and dimer of each naphthalenedicarboxylic acid were considered, and calculated proton chemical shifts for the potential monomer and dimer structures were compared to the experimental chemical shifts to find the weighted average structure that best fit the experimental shifts. Calculated carbon chemical shifts were also compared to experimental values. The chemical shift comparison and calculated energies indicate that π-stacked dimers are not likely to contribute significantly to the dimer structure of any of the three naphthalenedicarboxylic acid isomers studied.

Synthesis of naphthalenecarboxylic and naphthalenedicarboxylic acids from naphthalene, carbon tetrachloride, and alcohols in the presence of iron catalysts

Alkyl naphthalenecarboxylates and dialkyl naphthalenedicarboxylates have been synthesized by reactions of naphthalene and its derivatives with alcohols and carbon tetrachloride in the presence of iron catalysts.

Enhanced hydrophobic MIL(Cr) metal-organic framework with high capacity and selectivity for benzene VOCs capture from high humid air

A novel enhanced hydrophobic MIL(Cr) metal-organic framework was obtained by using naphthalene dicarboxylic acid as ligand and its adsorption equilibrium, diffusion kinetics and competitive adsorption for benzene and water were investigated systematically. Results show that: (1) the MIL(Cr)-Z1 possessed similar crystal structure and morphology to the MIL(Cr)-101. It had high surface area of 3008m2/g with smaller window apertures (6.9Å) and pore cages (23.3Å) than MIL(Cr)-101; (2) it had high benzene uptake of ∼7.0mmol/g with the isosteric heat of ∼51kJ/mol and high benzene diffusivity (30–40 times quicker than water molecules); (3) it showed an improved hydrophobic property with very low adsorbed amount for water vapor, only about 9.84mmol/g and 13% of that on MIL(Cr)-101 at 80 RH% and 298K; (4) breakthrough curves show that MIL(Cr)-Z1 had high working capacity for benzene, which was 58% higher than that of MIL(Cr)-101 at 60 RH%. Thus, high adsorption capacity and selectivity for benzene VOCs make enhanced hydrophobic MIL(Cr)-Z1 a promising candidate for benzene VOCs capture under high-moisture environments.

Iron-naphthalenedicarboxylic acid gels and their high efficiency in removing arsenic(v).

Metal-organic gels (MOGs) of three-dimensional (3D) networks comprising nanosheets of ∼30 nm thickness and square-micrometer in size were easily produced via coordination interactions of iron (Fe(3+)) and 1,4-naphthalenedicarboxylic acid (NDC). Such MOGs exhibit ultrahigh removal of arsenic(v) in water, with the adsorption capacity of 144 mg g(-1), dramatically superior to those of the recently reported Fe-based inorganic and organic adsorbents.